One-Step Relativistic Driven Similarity Renormalization Group Multireference Perturbation Theory

Abstract

We present an efficient implementation of a one-step relativistic second-order multireference perturbation theory based on the multireference driven similarity renormalization group (MR-DSRG) using the exact two-component (X2C) Hamiltonian, which we denote X2C-DSRG-MRPT2. We show that the X2C-DSRG-MRPT2 method can accurately capture spin--orbit coupling (SOC) effects in the electronic structure of strongly correlated systems containing elements across the periodic table. We further demonstrate that the X2C-DSRG-MRPT2 method, through its variational treatment of SOC effects, can yield spin--orbit splittings with mean absolute percentage errors consistently below 7% with respect to experimental values for systems containing up to sixth row elements. With its modest computational scaling (fifth power in system size) and high accuracy, X2C-DSRG-MRPT2 provides a promising avenue for the routine treatment of relativistic effects in strongly correlated molecular systems.